Printing inks



Patented Nov. 20, 1945 UNITED STATES PATENT OFFICE PRINTING INKS tion of New York N Drawing. Application July 26, 1944,

Serial No. 546,738

6 Claims. ,(Cl. 10630) This invention relates to printing inks of the quick drying type, particularly those inks which are dried rapidly by the application of steam to the freshly printed web or sheet affording prints which are rub-proof and which will not offset when rewound or stacked. The invention relates especially to steam-setting inks capable of satisfactorily printing half-tone illustrations.

Steam-setting inks have been described heretofore. Usually such inks consist of pigments suspended in vehicles consisting of a water-insoluble resin dissolved in a liquid polyglycol such as diethylene glycol. The inks are dried by the action of steam which causes water to dissolve in the film, thereby precipitating the water-insoluble resin.

In a co-pending application of Kroeger and OConnor Serial No. 466,672, filed November 23, 1942, steam-setting inks consisting of pigmented suspensions of water-soluble resins in organic solvents are described. These inks have the advantage over water-insoluble resin systems in that they are not set or dried prematurely even by a relative humidity of 100%, although when the film of ink on paper is subjected to steam, drying takes place in one second or less.

Inks of either of the classes described, that is, including a vehicle comprising either a waterinsoluble resin or a water-soluble resin, have certain disadvantages in respect to printing from plates containing fine half-tone screen areas. The prints become progressively more specked or filled in as the printing operation continues, with the result that the number of satisfactory impressions is low and frequency of wash-ups so great as to make the inks commercially impractical for half-tone printing. Waste of paper and of time are particularly to be avoided in printing operations.

The half-tone screen plate is made up of a large number of small, uniformly spaced dots or projections raised above the surface of the intervening areas of the plate. The flat top surfaces of these projections carry' the ink, thus producing when printed an image of the surface of the projections on the paper. A typical plate may have a 120-line screen, that is, any square inch of the screen area will have 120 dots or projections on a side, or a total of approximately 14,400 projections per square inch.

In any normal printing operation there is a quantity of. dust, lint, paper fibres and pigment particles which collect on the plate, and unless removed they will pack into the recesses between the dots until sumcient material is collected to bridge the opening between two or more dots. This bridged-over group of dots then transmits ink to the paper, and the result is a distinct speck in an otherwise uniformly printed area of smaller dots. As this process is repeated, the print takes on a typical dirty, rough appearance which is highly objectionable. The screens normally used in commercial half-tone printing var from to 133 lines per linear inch. 'As might be expected, difficulty with specking" or fill-up becomes more pronounced when the finer screens are used.

The older types of printing inks such as those made with linseed oil have the property of continually cleaning the plate of adherent dust, lint, fibers and pigment. These materials are carried back to the ink fountain where they are deposited and held. At the end of a long printing run, a substantial quantity of such materials may be found in the bottom of the fountain. Steamsetting inks made with resins dissolved in liquid polyglycols as solvents have very little tendency to behave in the manner described with respect to oil inks. The lint and dust which collect on the plate are not removed by the ink and remain in the recesses of the screen, eventually causing the difficulties hereinbefore mentioned.

It is the object of the present invention to provide improved inks of the steam-setting type which are not subject to the disadvantages set forth.

Other objects and advantages of the invention will be apparent as it is better understood by reference to the following specification, in which the preferred embodiments of the invention are described.

We have discovered that by incorporating substantial proportions of pine oil or its equivalent in steam-setting inks containing either waterinsoluble or water-soluble resins dissolved in liquid polyglycols, a substantial improvement in the printing properties of the ink is effected so that the improved inks print satisfactorily from half-tone screens without substantial specking or fill in. Pine oil is a liquid material of commerce derived from pine gum. It has a boiling range (5-95%) from approximately C. to pproximatel 225 C. and consists principally of borneol, isomers of terpineol and fenchyl alcohol together with smaller proportions of terpene hydrocarbons. It is usually obtained in the manufacture of gum or wood rosin. As supplied commercially, pine oil is a clear, colorless to faint yellow oily liquid which is soluble in a wide range of organic solvents, but insoluble in water. It has a characteristic pungent odor.

As an equivalent of pine oil, we have found that mono-terpinyl ethylene glycol ether is satisfactory. This compound is likewise a well known article of commerce, easily obtainable and having characteristics somewhat similar t those of pine oil and particularly in respect to its efiect when used in ink compositions.

The proportion of pine oil or its equivalent in the ink can vary between relatively wide limits. A sutlicient amount must be used to produce the desirable cleanliness of printing, but on the other hand the amount should not be so large as to interfere seriously with the speed of steam drying. Pine oil, being insoluble in water, has a tendency to prevent the introduction of moisture into the printed film when used in large amounts. A satisfactory guide in the amount of pine oil or its equivalent to be used is approximately 1 part for each 3 parts of liquid polyglycol. From 7% to 15% by weight of pine oil or its equivalent based on the total weight of the ink formulation will ordinarily assure excellent results, although variations beyond thi range may be desirable in certain instances due to the composition of a particular ink.

The details of the invention are illustrated more completely by the following examples, it being understood that these are merely illustrative, since ink formulations vary widely depending upon color, the nature of the pigment used, the resins and solvents used and other conditions.

Example I A sodium rosinate varnish was made as follows:

Parts Wood rosin, acid number-120.6 55.5 Diethylene glycol 37.3

Heat to 350 F. and hold until resin is dissolved. Cool to 150 F. Add:

' Parts 50% sodium hydroxide (aqueous) 7.2'

Stir until reaction is complete. miscible with water.

An ink was made according to the following formula:

This varnish was I Parts Milori blue 3.00 Carbon black 14.00 Calcium carbonate 8.00 Varnish as prepared above 46.40 Diethylene glycol 17.12 Pine 'oil 11.48

Example II The resin used was a rosin modified with an alpha beta unsaturated dibasic organic acid as described in the patent to Carleton Elli No. 2,063,542. This resin is known in the trade as Example III A urea-formaldehyde varnish was madeby taking a resin prepared by condensing urea with formaldehyde in water and interchanging solvents by vacuum distillation until the water was replaced with diethylene glycol. The varnish was soluble in water. The formulation was as fol- Example IV A varnish containing triethanolammonium rosinate, the rosin salt of triethanolamine, was made as follows:

Parts Wood rosin, acid number-120.6 52.3 Triethanolamine 12.5 Diethylene glycol 35.2

Heat to 300-320 F., hold till solution is clear, then cool. This varnish is miscible with water.

An ink was made from this varnish and had the following formula:

Parts Milori blue 3.00 Carbon black 14.00 Calcium carbonate 8.00 Varnish prepared above 51.40 Diethylene glycol 12.10 Pine oil 11.50

Following are two examples of inks including monoterpinyl ethylene glycol ether as the equivalent of pine oil:

Example V Parts Milori blue 3.00 Carbon black 14.00 Calcium carbonate 8.00 Teglac 127 28.50 Diethylene glycol 35.00 Mono-terpinyl ethylene glycol ether 11.50

Example VI Parts Milori blue 3.00 Carbon b1 ack 14.00 Calcium carbonate 8.00 Urea-formaldehyde resin 18.30 Diethylene glycol 45.04 Mono-terpinyl ethylene glycol ether 11.50 50% sodium hydroxide (aqueous) 0.16

The foregoing examples are black inks. The invention is equally applicable to the production of colored inks of great variety. .Any of the usual coloring materials may be employed in accordance with the standard practice of ink formulation. The following examples will sufiice to indicate typical formulations employing pine oil, it being understood that mono-terpinyl ethylene glycol ether may be substituted therefor.

Example VII We claim:

Parts 1. A printing ink comprising a suspension of Mllori blue 50.0 pigment in a vehicle consisting of a resin dis- Varnish of Example L 30.0 solved in a liquid polyglycol and a proportion of Diethylene glycol 8-6 a liquid selected from the class consisting of Pine oil -4 pine oil and mono-terpinyl ethylene glycol ether effective to prevent'fill-in" in half-tone plates 100-00 but insufficient to substantially interfere with the Example VIII speed of steam-drying of said ink.

Parts 2. A printing ink comprising a suspension of phthfllocyanme blue pigment in a vehicle consisting of a resin dis- F- of Example I 462 solved in a liquid polyglycol and a proportion of 1213115119118 glycol pine oil eifective to prevent fill-in in half-tone Pme 011 plates but insufilcient to substantially interfere with the speed of steam-drying of said ink.

. p 10000 3. A printing ink comprising a suspension of Example IX pigment in-a. vehicle consisting f a resin dis- Parts solved in a liquid polyglycol and a proportion of Chrome yellow mono-terpinyl ethylene glycol ether efiective to Val-n15? of f I prevent fill-in in half-tone plates but insufllg gg g f g yco 4 clent to substantially interfere with the speed of "f'"""'""""""' steam-drying of said ink.

100 00 4. A printing ink comprising a suspension of Example X pigment in a vehicle consisting of 'a resin dis- 7 Parts solved in a liquid polyglycol'and approximately Lake red C 25 00 7% to 15% by weight based on the total weight varnish a 5 3 46:40 of the ink of a. liquid selected from the class con- Diethylene 1712 sisting of pin oil and mono-terpimrl ethylene Pine on 1148 glycol ether to prevent fill-1n in half-tone plates. 4

100 00 5. A printing ink comprising a suspension of pigment in a vehicle consisting of a resin dis- The inks as described behave with respect to solved in liquid polyglycol and approximately dust. lint. fibers and P gment similarly to the 7% to 15% by weight based on the total weight older types of linseed oil links, that is to say, 3 of t k of pine 11,

the extraneous material, instead of collecting 6. A printing ink comprising a suspension of on the half-tone plates, is carried back to the pigment in a vehicle consisting of a, resin disink fountain. Specking and illl-inare subsolved in a liquid polyglycol and approximately stantially avoided even after long printing runs, 7% to 15% by weight based on the total weight permitting satisfactory impressions with the minimum of lost paper and wash-up time.

Various changes may be made in the details of the formulations without departing from the invention or sacrifing the advantages thereof.

of the ink of monoterpinyl ethylene glycol ether.

JOHN W. KROEGER. DANIEL J. O'CONNOR, JR. 

